BET-adsorption isotherm

Figure 5. Pore size distribution of sol-gel glass (described in text) as determined by nitrogen adsorption isotherm (BET).

Mesoporous silica, FSM-16, was prepared in the same way as the previous study [11]. The structure was confirmed by XRD pattern and N2 adsorption isotherm. BET surface area was 1025 m g. ... 

Figure 7.12. The BET-adsorption isotherm (BET AI), Eq. (7.70) showing for C>2 an inflection point and at the sorptive gas saturation pressure p = Ps(T) a singularity n — 00 indicating pore condensation and the appearance of a bulk liquid phase [7.1-7.5],...

The BET equation filled an annoying gap in the interpretation of adsorption isotherms, and at the time of its appearance in 1938 it was also hailed as a general method for obtaining surface areas from adsorption data. The equation can be put in the form... 

Equation XVII-78 turns out to ht type II adsorption isotherms quite well—generally better than does the BET equation. Furthermore, the exact form of the potential function is not very critical if an inverse square dependence is used, the ht tends to be about as good as with the inverse-cube law, and the equation now resembles that for a condensed him in Table XVII-2. Here again, quite similar equations have resulted from deductions based on rather different models. 

Adsorption isotherms in the micropore region may start off looking like one of the high BET c-value curves of Fig. XVII-10, but will then level off much like a Langmuir isotherm (Fig. XVII-3) as the pores fill and the surface area available for further adsorption greatly diminishes. The BET-type equation for adsorption limited to n layers (Eq. XVII-65) will sometimes fit this type of behavior. Currently, however, more use is made of the Dubinin-Raduschkevich or DR equation. Tliis is Eq. XVII-75, but now put in the form... 

Fig. 2.6 Adsorption of gases on silver foil. (a) BET plots h) adsorption isotherms. (Solid symbols are desorption points.) (Courtesy Davis, Dc Witt...

Fig. 2.20 Adsorption isotherms of carbon dioxide at — 78 5°C in TK 800 outgassed at 25 C and lOOO C (triangles). The BET monolayer is indicated as n on each isotherm.

The degree of uncertainty of 10 per cent or more, inseparable from estimates of specific surface from adsorption isotherms, even those of nitrogen, may seem disappointing. In fact, however, attainment of this level of accuracy is a notable achievement in a field where, prior to the development of the BET method, even the order of magnitude of the specific surface of highly disperse solids was in doubt. The adsorption method still provides the only means of determining the specific surface of a mass of non-... 

Fig. 3.Z3 Adsorption isotherm of n-butane at 273 K on a sample of artificial graphite ball-milled for 192 b. The shoulder F appeared at a relative pressure which was the same for all six samples in the first milling run, all six in the second milling run, and also for two of the milled samples which had been compacted. The milling time varied between 0 and 1024 h, and the BET-nilrogen areas of the surfaces between 9 and 610 m g ...

Fig. 4.29 Adsorption isotherms of water vapour on caldte, after being balt-milted for different periods (A, B, C) and on precipitated calcium carbonate (D). Period of milling (A) 1000h (B) ISOh (C) 22h outgassing temperature 2S°C. Isotherms A, B and C (but not D) all showed extensive low-pressure hysteresis, but for clarity the desorption branch is omitted. The amount adsorbed is referred to 1 m of BET-nitrogen area. ...

It would be difficult to over-estimate the extent to which the BET method has contributed to the development of those branches of physical chemistry such as heterogeneous catalysis, adsorption or particle size estimation, which involve finely divided or porous solids in all of these fields the BET surface area is a household phrase. But it is perhaps the very breadth of its scope which has led to a somewhat uncritical application of the method as a kind of infallible yardstick, and to a lack of appreciation of the nature of its basic assumptions or of the circumstances under which it may, or may not, be expected to yield a reliable result. This is particularly true of those solids which contain very fine pores and give rise to Langmuir-type isotherms, for the BET procedure may then give quite erroneous values for the surface area. If the pores are rather larger—tens to hundreds of Angstroms in width—the pore size distribution may be calculated from the adsorption isotherm of a vapour with the aid of the Kelvin equation, and within recent years a number of detailed procedures for carrying out the calculation have been put forward but all too often the limitations on the validity of the results, and the difficulty of interpretation in terms of the actual solid, tend to be insufficiently stressed or even entirely overlooked. And in the time-honoured method for the estimation of surface area from measurements of adsorption from solution, the complications introduced by... 

Surface areas are deterrnined routinely and exactiy from measurements of the amount of physically adsorbed, physisorbed, nitrogen. Physical adsorption is a process akin to condensation the adsorbed molecules interact weakly with the surface and multilayers form. The standard interpretation of nitrogen adsorption data is based on the BET model (45), which accounts for multilayer adsorption. From a measured adsorption isotherm and the known area of an adsorbed N2 molecule, taken to be 0.162 nm, the surface area of the soHd is calculated (see Adsorption). 

The development of microporosity during steam activation was examined by Burchell et al [23] in their studies of CFCMS monoliths. A series of CFCMS cylinders, 2.5 cm in diameter and 7.5 cm in length, were machined from a 5- cm thick plate of CFCMS manufactured from P200 fibers. The axis of the cylinders was machined perpendicular to the molding direction ( to the fibers). The cylinders were activated to bum-offs ranging from 9 to 36 % and the BET surface area and micropore size and volume determined from the Nj adsorption isotherms measured at 77 K. Samples were taken from the top and bottom of each cylinder for pore sfructure characterization. 

During ball milling the mean particle diameter, d, gas adsorption isotherm specific surface area (BET) and contamination (wt% contaminant) conform to the general law ... 

The reason for enhancement of adsorption performance of PA/AC was considered to be due to combination effect of increase of BET surface area and chemical modification by the treatment with PA. Consequently, lwt%-PA/AC was determined to be a best candidate as an adsorbent for removing benzene, toluene, p-xylene, methanol, ethanol, and iso-propanol. Therefore, lwt%-PA/AC was used as the adsorbent to investigate the adsorption isotherm, adsorption and desorption performance. 

The principle underlying surface area measurements is simple physisorb an inert gas such as argon or nitrogen and determine how many molecules are needed to form a complete monolayer. As, for example, the N2 molecule occupies 0.162 nm at 77 K, the total surface area follows directly. Although this sounds straightforward, in practice molecules may adsorb beyond the monolayer to form multilayers. In addition, the molecules may condense in small pores. In fact, the narrower the pores, the easier N2 will condense in them. This phenomenon of capillary pore condensation, as described by the Kelvin equation, can be used to determine the types of pores and their size distribution inside a system. But first we need to know more about adsorption isotherms of physisorbed species. Thus, we will derive the isotherm of Brunauer Emmett and Teller, usually called BET isotherm. 

What information can be obtained from a BET adsorption isotherm ... 

The BET surface area values are also reported with the distribution of porosity between microporosity (pore diameter <1.8 nm) deduced from N2 adsorption isotherms (t-curves) and mesoporosity (pore diameter > 1.8 nm). The following trend is observed for high atomic M/HPA ratio used for the precipitation, the precipitates exhibited high surface area mainly due to microporosity. However, depending on the nature of the coxmter cation and also of the previous ratio values, the textural characteristics were not similar. In particular, it is interesting to note the presence of mesopores for (NH4)2.4P, CS2.9P, CS2.7P and Cs2.4Si samples. 

Catalyst characterization - Characterization of mixed metal oxides was performed by atomic emission spectroscopy with inductively coupled plasma atomisation (ICP-AES) on a CE Instraments Sorptomatic 1990. NH3-TPD was nsed for the characterization of acid site distribntion. SZ (0.3 g) was heated up to 600°C using He (30 ml min ) to remove adsorbed components. Then, the sample was cooled at room temperatnre and satnrated for 2 h with 100 ml min of 8200 ppm NH3 in He as carrier gas. Snbseqnently, the system was flashed with He at a flowrate of 30 ml min for 2 h. The temperatnre was ramped np to 600°C at a rate of 10°C min. A TCD was used to measure the NH3 desorption profile. Textural properties were established from the N2 adsorption isotherm. Snrface area was calcnlated nsing the BET equation and the pore size was calcnlated nsing the BJH method. The resnlts given in Table 33.4 are in good agreement with varions literature data. 

Conventional bulk measurements of adsorption are performed by determining the amount of gas adsorbed at equilibrium as a function of pressure, at a constant temperature [23-25], These bulk adsorption isotherms are commonly analyzed using a kinetic theory for multilayer adsorption developed in 1938 by Brunauer, Emmett and Teller (the BET Theory) [23]. BET adsorption isotherms are a common material science technique for surface area analysis of porous solids, and also permit calculation of adsorption energy and fractional surface coverage. While more advanced analysis methods, such as Density Functional Theory, have been developed in recent years, BET remains a mainstay of material science, and is the recommended method for the experimental measurement of pore surface area. This is largely due to the clear physical meaning of its principal assumptions, and its ability to handle the primary effects of adsorbate-adsorbate and adsorbate-substrate interactions. 

The measured NMR signal amplitude is directly proportional to the mass of adsorbate present, and the NMR signal versus pressure (measured at a fixed temperature) is then equivalent to the adsorption isotherm (mass of adsorbate versus pressure) [24-25]. As in conventional BET measurements, this assumes that the proportion of fluid in the adsorbed phase is significantly higher than the gaseous phase. It is therefore possible to correlate each relaxation time measurement with the calculated number of molecular layers of adsorbate, N (where N = 1 is monolayer coverage), also known as fractional surface coverage. 

The adsorption/desorption isotherms measured by NMR (equivalent to conventionally measured isotherms), extracted from two different regions of the imaging field of view corresponding to the two ceramics, are shown in Figure 3.5.9. Once these local isotherms are extracted, they are simply the local adsorption for that point in space contained within the material, measured non-invasively and non-destructively. Conventional analysis techniques for adsorption isotherms (such as BET theory) can therefore be applied to the data, to determine the microstructural properties corresponding to that isotherm curve. 

Tab. 3.5.1 BET results obtained using conventional bulk N2 and NMR spatially resolved C4Fg adsorption isotherms.

The support and the catalysts were characterised by means of nitrogen adsorption, XPS, TPD and SEM. The nitrogen adsorption isotherms were determined at 77 K in a Coulter Omnisorp 1000 CX equipment, and were analysed by the BET equation (SBet), and by the t-plot for mesopore surface area (Smeso) and micropore and mesopore volume (Vmicr0, Vmeso), using the standard isotherm for carbon materials. The catalyst samples were previously outgassed at 120 °C. 

Specific surface areas are then obtained by dividing by the weight of catalyst employed in the experiments in question. It should be pointed out, however, that it is the BET adsorption isotherm that is the basis for conventional determinations of catalyst surface areas. (See Section 6.2.2.)... 

If one restricts the number of layers of adsorbate that may be stacked up, as would be the case in the very narrow capillaries of a porous catalyst, the BET analysis must be modified to allow for this. If n is the number of permissible layers, it can be shown that the adsorption isotherm becomes ... 

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